Cement and Concrete Research, Vol. 24, No. 4, pp.

605-612, 1994
Pergamon Copyright © 1994 Elsevier Science l..,td
Printed in the USA. All rights reserved
0008-88,46/94 $6.00+.00

0008-8846(94)E0002-F

EFFECT OF MOISTURE ON FRACTAL DIMENSION

AND SPECIFIC SURFACE OF HARDENED CEMENT PASTE
BY SMALL-ANGLE X-RAY SCATTERING

R.E. Beddoe and K. Lang

Baustoffinstitut - Werkstof~hysik
Technische Universit~t, W-8000 Miinchen, Germany

(Communicated by F.H. Witmaann)

(Received July I, 1993)

ABSTRACT
Finely divided fumed silica (Aerosil) has been used as a model substance to inter-
pret the change in fractal dimension and specific surface of hardened cement paste
(hcp) with relative humidity. Hcp is essentially a surface fractal at relative hu-
midities below ca. 40% where the specific surface diminishes as surface area is
lost around the gel particle contact points during adsorption. A "smoother" surface
of lower fractal dimension results. Above ca. 40 %rh the disjoining pressure opens
up the entangled hcp gel structure to produce a more mass fractal structure of
higher internal surface area.

Introduction

The adsorption of water on the large internal surface of hardened cement paste influences
strongly the interaction torces between the gel particles. Thus according to the Munich Model
/I,2/ drying shrinkage, creep, Young's modulus and strength are governed by changes in
surface free energy of the gel particles at relative humidifies below ca. 40% and by the action
of the disjoining pressure at higher relative humidities. Whereas hcp shrinks continuously
during drying, the specific surface of hcp measured by small-angle x-ray scattering (SAXS)
decreases down to relative humidities around 40%. and thereafter increases at lower relative
humidities/3,4/. On adsorption, the reverse process occurs with hysteresis. Fig. 1 shows typi-
cal data tbr a German Portland and a blast furnace cement. The behaviour of the specific sur-
face below 40 %rh is also linked with the increases in compressive strength and Young's
modulus which Setzer and Wittmann /5/ explained by an increase in surface energy.

in view of the present data and similar SAXS observations by Bier and Hilsdorf /3/ on hcp and
porous aluminium oxides, the increase of the specific surface below 40 %rh appears to be
related to particle size. Thus the scattering from a model substance, fumed silica, with differ-
ent known particle sizes has been studied and compared with hop data.

605
606 R.E. Beddoe and K. Lang Vol. 24, No. 4

300
I I
• HO Z 35 L, desorption

250 -1 - - -- HOZ 35 L, adsorption Fig. 1

!
I ¢ PZ35F'des°rpti°n
oe_-200 -~ - - - - PZ 35 F, adsorption Specific surface of hcp
/
(w/c 0.5) made with Port-
land (PZ 35 F) and blast
~
u
150
furnace (HOZ 35 L) ce-
ments as a function of rel-
100
ative humidity.

50
0 0.2 0.4 o.6 0.8
Relative humidity

Experimental Procedure
Aerosil

The commercial fumed silicas Aerosil OX50, 130 and 200 as supplied by Degussa, Frankfurt
a.M., Germany were used. According to the manufacturer these silicas have BET nitrogen
specific surfaces of 50, 130 and 200 m2/g and mean particle diameters of 40, 16 and 12 nm.
The spherical particles are surface active due to silanol groups (3/nm2) which can tbrm hydro-
gen bonds.

Following Bier and Hilsdorf/3/, special holders were constructed which contained the samples
in a vacuum tight sandwich between two high purity aluminium x-ray windows 0.1 mm in
thickness.

The sample holders were filled with Aerosil pastes of suitable consistency and dried over blue
gel in a desiccator. The SAXS intensity was then measured using an evacuated Kratky camera
with Cu-K~ radiation from an x-ray tube operating at 40 kV and 20 mA. Intensities l(h) were
recorded by step scanning with a proportional detector over 300 scattering angles 20 corres-
ponding to scattering vectors h (=4n sin(0)/X where X is the wavelength of the radiation) be-
tween 0.06 and 1.3 nm-1 .

This procedure was repeated after transferring the samples complete with open holders to des-
iccators at 12, 33, 43, 61, 75, 90, 96 and 100 %rh. The weight change of a parallel sample
batch was monitored to ensure that the samples were in equilibrium with each relative
humidity.

Hardened Cement Paste

Samples measuring 30"10"0.4 mm3 were sawn out of hcp plates which had been stored at
least six months in a saturated Ca(OH)2 solution. The SAXS intensity from samples made with
HOZ 35 L or PZ 35 F at w/c ratios between 0.4 and 0.7 was measured during stepwise
desorption and adsorption.
Vol. 24, No. 4 FRACTAL DIMENSION, MOISTURE, SMALL ANGLE X-RAY SCATI'ERING 607

Water saturated and dry samples made from five different cements have also been investigated.
The pastes were mixed at w/c ratios of 0.4 and 0.6 and the samples prepared as above.

Data Evaluation

Alter correcting the scattering data for parasitic and background scattering, the specific surface
S was calculated using Eqn. 1. Further details are available in an earlier publication/4/.
3C 3C
S = 4 ~ Si(h)hdh / p ~l(h) dh (1)
O O

The matrix density p and porosity • of the pastes were determined using a pyknometer.

TABLE !

Porosity and matrix density of Aerosil pastes

Aerosil Matrix density g/m 3 Porosity

OX50 2.28 0.65
130 2.32 0.86
200 2.26 0.84

Small-angle scattering can be used to investigate fractal materials if the scattering obeys a
power law l(h) - h-q. Bale and Schmidt /6/ have derived an expression for the power law for
surface fractals of dimension Ds. For a slit-smeared small-angle scattering curve the scattering
intensity is

I(h) - h-(5-Ds), 2 < Ds <3. (2)

Similarly, tbr mass fractals of dimension D m / 7 /

l(h) - h(1-Dm), Dm<3. (3)

The fractal dimension can be determined from log-log plots of the scattering curves. Depend-
ing on the values of D s and Dm, it is possible to distinguish between surface and mass fractals
/8/.

Results and Discussion

Aerosil

Examples of typical SAXS curves can be seen in Fig. 2. Fig. 3 shows the resulting specific
surfaces of Aerosii OX50, 130 and 200 during adsorption. Similar to hcp, a decrease in spe-
cific surface is apparent whose degree depends clearly on the specific surface of the dry ad-
sorbent. The water vapour adsorption isotherms obtained fi'om the parallel sample batch are in
Fig. 4.
608 R.E. Beddoe and K. Lang Vol. 24, No. 4

1.00E+07
96 %th (1"1000)
1.00E+06
61%m 0"I00) Fig. 2
1,00E+05
33 %rh (1"10) SAXS curves for Aerosil 130
1,00E+04 at different relative humidities
during adsorption. For better
~ 1,00E+03 clarity the intensities have been
multiplied as indicated in the
1.00E+02

1.00E+01
~ .~

%
brackets.

1,00E+00
0.01 0.1
Scatledng vector, nm -~

250
I .
Aerosi1200
--- .... -l --___m_

(m
Fig. 3 200
Aerosil 130
, A J. L ..,..
Specific surface of Aerosil as a
function of relative humidity
during adsorption. The curves ~15o
were calculated with Eqn. 4

Aerosil OX ~0
B__
• t-'--.- L.
100
0 0.2 0.4 0.6 0.8 1
R e l a t i v e humidity

2,.50E-01
,
= -- AerostlOX50
/
2,00E-01 Aerosil '130 /
" Aerosi1200
Fig. 4
£m
1,50E-01
8 Room temperalure water va-
Q.
o pour adsorption isotherms of
"o 1,00E-01
<E Aerosil.

5o00E-02

~ .
0.00E +00
0 02 0,4 0.6 0.8
Relative humidity
Vol. 24. No. 4 FRACTAL DIMENSION. MOISTURE, SMALL ANGLE X-RAY SCATTERING 609

Estimated values for the specific surface area based on BET analysis are 11, 39 and 71 m2/g
tbr Aerosil OX50, 130 and 200, respectively. A small degree of hysteresis was observed at
relative humidities above 50% when the samples were subsequently redried.

It is well known that the panicles in highly dispersed solids, particularly inorganic oxides, can
be cemented together through the agency of adsorbed water/9/. This leads to surthce loss at
the particle/particle .junctions and thus a lower specific surface of the aggregation.

In order to quantify this effect, the specific surface of Aerosil during adsorption has been cal-
culated using a simple model comprising a cubic array of spheres of radius R in contact along
the cubic directions. The specific surface is assumed to be at the water/air interface in the gaps
between the spheres. As the thickness ~ of the adsorbed layer increases surface area is lost
around the junction points according to

S = 3(R +'t)(R-2"r)/OpR 3, -t < R(-~-I). (4)

x was calculated using the expression published by Badmann et al. /10/for the statistical thick-
ness of the adsorbed layer as a function of relative humidity x. pp is the density of the Aerosil
panicles.

~(x) =0.385-0.189(ln(-In(x)) nm (5)

The curves in Fig. 3 were calculated using the particle diameters supplied by the manufacturer
and normalised to the values measured at 0 %rh. In spite of the crudeness of the model, the
general fit of the data is good. Thus although, like hcp, Aerosil swells during adsorption (we
estimated a total relative length change of 4"10 -3 tbr Aerosil 130), the decrease in specific
surface can be explained simply. We inter that this mechanism also accounts for the behaviour
of the specific surface of hcp at low relative humidities. Furthermore, a fit of the model to the
data in Fig. i produced panicle diameters of 10 nm which is approximately the mean size of
hcp gel panicles.

2.40
' • " " " " ".....~.Ae
• ro s d 20(
~ 2.3o ~ ~ Fig. 5

Surface fractal dimension of

Aerosil as a function of relative
humidity during adsorption.

,,] 2.10
\
2,00
0 0,2 0,4 0,6 0.8
Relative. humtdity
610 R.E. B e d d o e and K. Lang Vol. 24, No. 4

For all samples and relative humidities, the scattering curves of the Aerosil pastes obey a
power law h-q with 2 . 6 < q < 2 . 9 over a scattering vector range between 0.2 and 0.7 nm -1.
Moist Aerosil gel is theretbre a surface fractal over a scale between approximately 9 and
31 nm. The behaviour of the surface fractal dimension during adsorption, determined from
Eqn. 2, is shown in Fig. 5.

The decrease in surface fractal dimension means that water molecules are preferentially ad-
sorbed on "rough" energetically favourable sites causing smoothing of the fractal surface. As
can be seen in the figure, this smoothing effect is stronger tor the higher initial fractal dimen-
sions determined tbr the finer silicas.

Hardened Cement Paste

The power law for the scattering from hcp made with HOZ 35 L or PZ 35 F is related clearly
to moisture content, Fig. 6. Depending on the value of p tbr a particular scattering curve,
either the surface or the mass fractal dimension was calculated according to Eqns 2 or 3, re-
spectively. Both fractal dimensions of the blast furnace cement are combined in Fig. 7. The
Portland cement exhibits essentially the same behaviour.

1.00E ~ C,'7 2,5

1.00E +06
HOZ. 43 %rh

HOZ: 12 %th
%rh %
,~ 1.00E +05
HOZ. O %dl ~ ,

1,00E+04

1,00E + 03
PZ 100

|
,I
IL

i
.~
lo 2.5
,5
~
•

.=
w/C 0.5
desorption

w/c 0.5
adsorption
w/c 0.7
\
desorption

~ w/c 0.7
m adsorption
1.00E + 02

...... r~,
1.00E+01 ...... i i i

0.01 0,1 0.2 0,4 0.6 0.8

Scattering vector, nm -1 Relative humidity

Fig. 6 Fig. 7

Examples of SAXS curves for hcp Behaviour of the fractal di-

made with HOZ 35 L, w / c = 0 . 6 , mension of HOZ 35 L hcp at
or PZ 35 F, w / c = 0 . 5 , at various w/c ratios 0.5 and 0.7 during
relative humidities. The intensities desorption and adsorption. D s
are multiplied by arbitrary scaling was calculated for q > 2 and
factors. D m tbr q < 2 .
Vol. 24, No. 4 FRACTAL DIMENSION, MOISTURE, SMALL ANGLE X-RAY SCATI'ERING 611

Between 0 %rh and roughly 40 %rh (depending on hysteresis effects), the trend of the curves
is towards surface fractals of lower dimension, in view of the above considerations on Aerosil,
the reduction in D s conlorms with selective adsorption of water molecules on the internal sur-
lace of hcp which leads to a less fractal (smoother) inner surface whose area decreases accord-
ing to the model proposed earlier.

However, above roughly 40 %rh the trend is towards a mass fractal structure. Thus in this re-
gion, the action of the disjoining pressure appears to open up "the entangled and branching in-
ner structure of the hcp gel. This structure was initially inaccessible for the water or air neces-
sary fi)r the electron density scattering contrast which reveals the more open fractal structure
with a larger specific surface. A similar, but reversed, process occurs during hydration.
Kriechbaum et al. /I 1/used SAXS to follow the change in fractal dimension between 1 and 28
days of hydration. They attributed an increase in D m from 1.9 to 2.8 in this period to the tbr-
mation of a more compact and closed structure.

Fig. 8 compares specific surfaces and mass ffactal dimensions of water saturated and dry hcp
made with a selection of cements. The different results may be explained by variation in de-
gree of hydration and composition of the clinker pha~s. At 0% and 100 %rh the surface of
electron density contrast is at the matrix/air and the matrix/water interfaces, respectively. Thus
additional contributions fn)m the water/air interlace at intermediate relative humidities are not
present.

These and the above results are for first drying. Subsequent desorption/adsorption cycles may
cause an irreversible loss of internal surface.

m w/c 0.4. wet Im w/c 0.6 wet l'-] w/c 0.4, dry row/cO.6 dry ]

350

300

250
Fig. 8
150
Specific surfaces and
mass fractal dimensions
5O
of hcp made with differ-
ent cements mixed at w/c
PZ 35 F (1) PZ 35 F (2) PZ 45 F PZ 55 F HOZ 35 L
3.00 . ratios of 0.4 and 0.6.
Values are shown for dry
co 2.50 and water saturated ,sam-
2.0o ples.

0,511,

0.00
PZ 35 F (1) PZ 35 F (2) PZ 45 F PZ 55 F HOZ 35 L
612 R.E. Beddoe and K. Lang Vol. 24, No. 4

Conclusions

The decrease in specific surface of hcp during adsorption up to ca. 40 %rh can be explained by
surface loss around contact points between gel particles as the thickness of the adsorbed layer
increases. Hcp is a surface fractal at these humidities, whose dimension decreases as water
molecules are adsorbed. Above ca. 40 %rh the disjoining pressure causes hcp to possess a
more open and mass fractal structure of higher internal surface area.

The significance of surface interactions at low humidities and the disjoining pressure at high
relative humidities was recognised earlier in the Munich Model /1,2/. The fractal nature of hcp
thus emerges as an important factor when considering the effect of moisture on the mechanical
properties and structure of hcp.

Acknowledgements

Special thanks are extended to Prof. M.J. Setzer at the University of Essen in Germany for his
help and advice.

References

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2. F.H. Wittmann, DAfStb 290 (1979)
3. Th. Bier, H.K. Hilsdorf, Anwendung der R6ntgen-Kleinwinkelstreuung zur Bestim-
mung der Porenstruktur von Baustoffen, DFG report, Univ. of Karlsruhe, Germany,
1985
. J.J. V61kl, R.E. Beddoe, M.J. Setzer, Cem. Concr. Res. 17, 81 (1987)
5. M.J. Setzer and F.H. Wittmann, Appl. Phys., 3,403 (1974)
6. H.D. Bale and P.W. Schmidt, Phys. Rev. Lett. 5_33,596 (1984)
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(1984)
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